CNSL-based hydrocarbon resins, preparation and uses thereof

ABSTRACT

The present invention is directed to resins made from cashew nutshell liquid and vinyl hydrocarbons and processes for manufacturing the resins. These resins exhibit lower viscosity than the phenol-based homologs. They also exhibit good compatibility with a wide range of solvents, mineral and natural oils, epoxy curing agents, liquid epoxy resins, and polymers, which make them suitable additives as non-reactive diluents for solvent-free coating formulations; tackifiers for structural adhesive, pressure sensitive and hot-melt adhesives; stabilizers for lubricants, fuel and polymer formulations; plasticizers for thermoplastic polymers and processing aid for rubber compounding and stabilizers for respective rubber artifacts. These resins are also valuable precursors for the manufacture of epoxy resins and polyols for coating, adhesive and composite formulations exhibiting ameliorated performance in water repellency, anti-corrosion, and fast hardness development during cure.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/888,209 filed on Oct. 8, 2013, the contents of which areincorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The invention generally relates to resins made from cashew nutshellliquid and vinyl hydrocarbons, and processes for manufacturing theresins.

BACKGROUND OF THE INVENTION

Phenol-modified hydrocarbon resins are widely used in coatings andadhesive formulations, and also widely used in the manufacturing ofrubber products. These resins improve the compatibility of theingredients in such formulations. In addition, the resins provideimproved chemical and weathering resistance to finished productsdesigned to perform under harsh environmental conditions, such as widevariation of temperature, oxidation by air, and light exposure. Otheradvantages include the substantial improvement of the adhesiveproperties in coating and adhesive formulations.

Phenol-modified hydrocarbon resins encompass a wide range of productsproduced by the reaction between phenols and vinyl aliphatic andaromatic monomers. In general, the composition of these resins is quitecomplex, which can be simply characterized by a mixture of monomeric andpolymeric components bearing distinct chemical functionalities. Forinstance, the reaction of unsubstituted phenol with vinyl hydrocarbonmonomers, such as styrene, alpha-methylstyrene, vinyltoluene, indene,coumarone, or any other similar vinyl monomers, or a mixture thereof,catalyzed by strong acids, produces liquid to wax-like resins containingvariable amounts of short polymers of vinyl monomers, in addition to thealkylated phenol components. The polymer fraction is mostly composed ofcyclic dimers and trimers of the vinyl monomers, with small amounts ofrespective linear oligomers. The alkylated phenol fraction is alsomulticomponent, as it contains variable amounts of monosubstituted,disubstituted, and trisubsituted phenolic compounds. The compositions ofthese resins can be controlled by careful adjustments of the reactionconditions. However, the most significant factor to control the desiredphysico-chemical properties is the judicial selection of structuralvariations on the phenol and on the vinyl hydrocarbon monomer buildingblocks. Mixtures of phenols and/or vinyl monomers are very oftenemployed to achieve the right balance of polarity, solubility, andfluidity, which is intimately related to the hydroxyl functionality, thecontent of aromatic, hydrophobic moieties, and polymer fractions, inaddition to the molecular weight distribution. For this purpose, it is acommon practice to incorporate small portions of an alkyl-substitutedphenol to the reaction mixture. The most commonly used alkyl-substitutedphenols are ortho- and para-tert-butylphenol, octylphenol, andnonylphenol. These phenols can be produced in-situ, prior to or afterthe reaction with the intended vinyl monomers. These variations in theprocess can add cost and complexity to the manufacturing of such resins.In addition, it can be more difficult to stabilize the process andminimize the variability between batches as the number of steps and rawmaterials are increased.

Cashew nutshell liquid (CNSL) contains a large concentration of cardanoland cardols, a natural source of meta-substituted alkylated phenols andresorcinols. CNSL is relatively low cost, and it is a globally availablebio-renewable commodity, which makes it an ideal building block for themanufacturing of phenol-modified hydrocarbons resins. Due to thestructure of the components of CNSL, the hydrocarbon resins can bemanufactured with fewer steps and/or raw materials.

Among the advantages of cardanol-based hydrocarbon resins are lowviscosity, improved solubility with organic solvents, very low cloudpoints, and compatibility with a great number of resins and polymerformulations.

SUMMARY OF THE INVENTION

The present disclosure relates to resin compositions comprisingcardanols obtained from Cashew Nut Shell Liquid (CNSL) and processes formaking the resins. In one embodiment, the resins may be comprised ofvinylated cardanols and vinylated cardols, wherein the cardanols andcardols are obtained from CNSL, as well as hydrocarbon cyclic dimers.The resin may include one or more additional polymers.

The resin may be manufactured by combining in a reactor vessel aquantity of CNSL, an acid catalyst, and a vinyl monomer, and maintainingthe reactor vessel at a predetermined temperature for a predeterminedperiod of time to achieve the desired degree of polymerization. As oneskilled in the art will recognize, the proportions of the components tobe used, the temperature and the time may be adjusted as desired toachieve a desired degree of polymerization of the components.

The resins may be used in coatings, as tackifiers, and for numerousother products that may use or include hydrocarbon resins.

DESCRIPTION OF THE FIGURES

For a better understanding of the present invention, reference is madeto the following detailed description of an exemplary embodimentconsidered in conjunction with the accompanying drawings.

FIG. 1 shows an exemplary cardanol molecule.

FIG. 2 illustrates generally the reaction mechanism for one embodimentof the disclosure.

FIG. 3 shows the effect of different concentrations of a commercialphenol-hydrocarbon resin and CNSL hydrocarbon resin on the viscosity ofa liquid epoxy.

FIG. 4 shows the results of a cross-hatch adhesion test on rusted S-36panels treated with a pigmented white epoxy base formulation comprisingCNSL hydrocarbon resin.

FIG. 5 shows a tested panel image of CNSL hydrocarbon system after 668hours salt spray exposure.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the present disclosure is directed to resins producedby the reaction between Cashew Nut Shell Liquid (CNSL) and respectivederivatives with vinyl hydrocarbons. The reaction may be promoted byacid catalysts. These resins are generally comprised of about 20-95% byweight of “vinylated” cardanols and cardols, about 1-40% by weight ofhydrocarbon cyclic dimers, and about 0-50% by weight of polymers, whichmay be a mixture of short chains composed of vinyl hydrocarbon monomersand cardanol units, with degree of polymerization of no less than 2 andno more than 10 repeating monomer units.

In certain embodiments, the CNLS hydrocarbon resins comprise about 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or95% by weight of vinylated cardanols and vinylated cardols. Any of thesevalues may be used to define a range for the percent by weight of thevinylated cardanols and vinylated cardols depending on the application.For example, the amount of vinylated cardanols and vinylated cardols inthe CNSL hydrocarbon resin may range from about 25% to about 90% byweight, from about 30% to about 85% by weight, or from about 40% toabout 80% by weight.

In certain embodiments, the CNLS hydrocarbon resins comprise about 1%,2%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40% by weight ofhydrocarbon cyclic dimers. Any of these values may be used to define arange for the percent by weight of the hydrocarbon cyclic dimers. Forexample, the amount of hydrocarbon cyclic dimers in the CNSL hydrocarbonresin may range from about 5% to about 35% by weight, from about 10% toabout 30% by weight, or from about 15% to about 25% by weight.

In certain embodiments, the CNLS hydrocarbon resin comprises vinylatedcardanols, vinylated cardols, and hydrocarbon cyclic dimers, and doesnot comprise any additional polymers. In other embodiments, the CNLShydrocarbon resin comprises about 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% by weight of one ormore additional polymers. Any of these values may be used to define arange for the percent by weight of additional polymers. For example, thepercent by weight of one or more additional polymers in the CNLShydrocarbon resin may range from about 1% to about 70%, from about 5% toabout 45%, or from about 10% to about 40%. In certain embodiments, theone or more additional polymers are linear oligomers of vinylhydrocarbon monomers and cardanols, with a degree of polymerization of2, 3, 4, 5, 6, 7 8, 9, or 10 repeating monomer units. Any of thesevalues may be used to define a range for the degree of polymerization ofthe additional polymers. For example the degree of polymerization of theadditional polymers may range from 2 to 10, 3 to 9, or 4 to 8 repeatingmonomer units.

In another embodiment, non-purified CNSL is reacted with vinylhydrocarbon monomers to make CNSL-based hydrocarbon resins. Non-purifiedCNSL is the raw product originated from the extraction process of thecashew shells. Depending upon the extraction procedure, the non-purifiedCNSL may contain relatively large amounts of cardols compared topurified CNSL. Also, depending upon the source, the total amount ofcardols in non-purified CNSL can be as high as 25% by weight.Non-purified CNSL may contain large amounts of cardol and cardanololigimers. The polymerization of cardols and cardanols can occur slowlyunder normal environmental conditions, although it can be accelerated byhigh temperature treatment, or it may be caused by oxidation processesduring the CNSL extraction procedure. Also, depending upon the processof extraction, anacardic acid can be present in relatively highconcentrations. The advantage of using non-purified CNSL is the lowercost of the raw material. The resins derived from non-purified CNSL cancontain relatively high amounts of polymer, between about 5-35% byweight of the total resin. In certain embodiments, the resins derivedfrom non-purified CNSL contain about 5%, 10%, 15%, 20%, 25%, 30% or 35%polymer by weight of the total resin. Any of these values may be used todefine a range for the percentage of polymer in the resin. For examplethe percentage of polymer in the resin may range from about 10% to about30%, about 15% to about 30%, or about 20% to about 25% of the totalresin. The main advantages of hydrocarbon resins made with non-purifiedCNSL are related to their low migration, high hydrophobicity, andtackifier features. The most appropriate applications are additives forsealants, building materials, structural adhesives, and in manufactureof compounded rubber products.

In another embodiment, purified CNSL is reacted with vinyl hydrocarbonmonomers to make CNSL-based hydrocarbon resins. Depending upon thepurification procedure, the purified CNSL will contain reduced amountsof cardols, preferably below about 5%, and very low content of polymerspecies, preferably no more than about 2%. Also, anacardic acid issubstantially completely removed from the CNSL. The major components ofpurified CNSL are the cardanol isomers, which are differentiated by thenumber of carbon double bonds on the side chain, as shown in FIG. 1 anddescribed in U.S. Pat. No. 6,229,054, the contents of which are herebyincorporated by reference in their entirety. The total cardanol contentis typically about 80 to 99% by weight, and is preferably about 85-99%,about 90-99% or about 95-99% by weight. The hydrocarbon resins made withpurified CNSL are light colored, and exhibit low viscosity. The contentof vinylated cardanols in the resins is typically about 20-99% byweight, and preferably about 50-95%, about 60-95%, about 70-95%, orabout 80-95% by weight. Among the advantages of hydrocarbon resins madewith purified CNSL are their light color, and anti-oxidant properties.These resins are particularly useful for coatings applications.

In yet another embodiment, highly purified CNSL is used. Depending uponthe purification procedure, highly purified CNSL may contain only traceamounts of cardols, and essentially no polymer components and anacardicacids. They are essentially very pure cardanol mixtures, composed ofonly cardanol isomers which are differentiated by the number of carbondouble bonds on the side chains. The total cardanol content is typicallyabout 96% to 100% by weight, and preferably about 97% to 99.9%, about98% to 99.9%, about 99% to 99.9%, or about 99.5% to 99.9% by weight.Depending upon the purification procedure the compositional distributionof the four cardanol isomers may vary greatly. In most cases, thecontent of cardanols with triene, diene, monoene, and saturated sidechains are about 30-45% by weight, about 15-25% by weight, about 30-45%by weight, and about 0-10% by weight, respectively. In special cases,the content of isomers bearing multiple carbon double bonds on the sidechains are intentionally depleted by means of physical separation orchemical reactions, to produce CNSL with better oxidation, colorstability, and higher thermal transitions. For such purpose, thecompositional distribution of cardanol triene, diene, monoene, andsaturated isomers are preferably about 0-5% by weight, about 0-10% byweight, about 70-95% by weight and about 0-15% by weight, respectively.

In another embodiment, the distillation residue from the manufacturingprocess of the purified CNSL or the highly purified CNSL, characterizedas a side stream, is also reacted with vinyl hydrocarbon monomers tomake hydrocarbon resins. Depending upon the purification procedure,these side streams contain very high amounts of polymer components, highcontents of cardols, and very low content of cardanols, and aresubstantially free of anacardic acids. The polymer content ischaracterized as a complex mixture of polymerized cardol and cardanols,normally caused by side chain polymerization, mostly throughisomerization and cycloaddition reactions. The polymer can alsooriginate from oxidative reactions. The molecular weight of the polymerfraction ranges from about 500 to 10,000 g/mol. The polymer level inthis CNSL is about 20-95% by weight, and preferably about 30-80%, 40-70%or 40-60% by weight. The hydrocarbon resins produced using these sidestreams exhibit very high viscosity and enhanced hydrophobic properties.The resin may be used as a rheology modifier, an impact modifier, atackifier, a plasticizer, a weathering stabilizer, and/or ananti-oxidant. They may also reduce cracking and brittleness ofthermoplastic and thermoset polymer formulations, and the products madefrom these polymers. Due to the high polymer content of these resins,they may also be used in applications where control of leachates,migration, VOC, and other restrictive regulatory controls are required.

In another aspect, for the purpose of this disclosure, chemicallymodified CNSL streams are reacted with vinyl hydrocarbon monomers tomake CNSL-modified hydrocarbon resins. Suitable chemical modificationscan be carried out on the aromatic ring reactive sites, or on the doublebonds of the side chains of the cardol, cardanols and anacardic acidscomponents.

Any of the aforementioned purified or non-purified CNSL may react withaldehydes and ketones promoted by acid catalysts to form polymers of thenovolac resin type. The same catalyst that converts CNSL substrates toCNSL hydrocarbon resins, can also promote the polycondensation reactionof cardol, cardanols or anacardic acids with aldehydes or ketones.Therefore, the CNSL-novolac-hydrocarbon resins can be made in one singlebatch process. The process can start with the production in-situ of thehydrocarbon resin, and then the polycondensation reaction is carried outwith aldehyde or ketones in a subsequent step. Alternatively, under thesame principle, the order of above steps can be reversed, in which casethe CNSL-novolac resin is made first as an intermediate, followed by thereaction with the vinyl hydrocarbon monomers in a subsequent step. Fromthe manufacturing perspective, the former manufacturing process is thesimplest one, and therefore the preferred one.

Any of the aforementioned types of CNSL may be catalytically reducedwith hydrogen under pressure and promoted by active metal catalysts toproduce a partially or completely saturated product. This hydrogenatedCNSL is allowed to react with vinyl hydrocarbon monomers promoted byacid catalysts to produce CNSL-based hydrocarbon resins featuring verylow color, high chemical resistance and stability in weatheringconditions. These hydrocarbon resins may be used in coatingformulations, or in polymer product compositions that are intended toresist intense exposure to natural light. Alternatively, thehydrogenation process can also be done after the reaction between anytype of CNSL stream and hydrocarbon vinyl monomers under similarconditions.

Any aforementioned CNSL-based hydrocarbon resins can be chemicallymodified afterwards, to attain special desirable features. As part ofthis disclosure, the carbon double bonds on the side chains of thecardanol in the aforementioned CNSL-based hydrocarbon resins can beepoxidized with hydrogen peroxide, or organic peroxides, or acombination of hydrogen peroxide and organic carboxylic acids. Thedegree of epoxidation can be selectively controlled by the reactionconditions, and by adjusting the substrate to peroxide feed ratios.These epoxidized CNSL-based hydrocarbon resins are suitable forlubricant compositions. The side double bonds can also be fullybrominated with molecular bromine or other suitable organic andinorganic brominating agents, to produce resins with flame retardantcharacteristics.

Other common phenols can also be incorporated in hydrocarbon resinsalong with the CNSL to make resins comprised of variable amounts of CNSLbuilding block in the final resin. These modifications may be useful forenhancement of specific desirable features. For instance, addition ofbisphenol-A to the reaction mixture produces resins with high glasstransition temperature. Lighter color, anti-oxidant properties, andlight stability are other common enhanced features that can be achievedby the addition of about 2-70% by weight, and preferably 5-50%, 5-40%,5-30% or 5-20% by weight of other simple synthetic phenols prior to orduring the reaction of CNSL with the hydrocarbon vinyl monomers to makethe respective blend of the desired CNSL and phenol based hydrocarbonresins. Examples of suitable phenols include, but are not limited to:phenol, nonylphenol, ortho-tert-butylphenol, para-tert-butylphenol,ortho-cresol, para-cresol, meta-cresol, technical grade mixture ofcresols, bisphenol-A, bisphenol-F, hydroquinone, resorcinol, catechol,butylhydroxytoluene, methoxyphenol, tert-butylcatechol.

Suitable vinyl hydrocarbon monomers used in the manufacture ofCNSL-based hydrocarbon resins are preferably the aromatic vinylmonomers, in which one or multiple alkene groups are linked directly toan aromatic hydrocarbon group, or to multiple aromatic groups that canbe fused together or linked by single carbon-carbon bonds. Examplesinclude, but are not limited to, styrene, alpha-methylstyrene,vinyltoluene (mixture of ortho, meta, and para isomers), indene,indene-coumarone streams from coal tar distillation,alpha-vinylnaphthalene, diisopropenylbenzene (and respective mixture ofortho- meta- and para-disubstituted isomers), the C9 fraction from apetroleum cracking process, divinylbenzene, and mixtures ofdivinylbenzene and ethylvinylbenzenes. Aliphatic and cycloaliphaticvinyl monomers can also be used alone or in a mixture with aromaticvinyl monomers. Examples of suitable aliphatic and cycloaliphatichydrocarbon vinyl monomers include, but are not limited to, isobutylene,butadiene, isoprene, pentadiene, cyclopendadiene, dicyclopentadiene,pinenes (alpha and beta isomers), limonene, cyclohexane,vinylcylohexane, and mixtures of unsaturated olefins from the so called“C5 fraction” originated from oil refineries.

Suitable catalysts for the preparation of CNSL-based hydrocarbon resinsmay be strong inorganic protic acids, including, but not limited to,sulfuric acid, hydrofluoric acid, hexaflyorophosphoric acid,tetrafluoroboric acid, perchloric acid, or a mixture thereof. Lewisacids are also another good alternative to the inorganic protic acids,as they are very effective promoting Friedel-Crafts reactions, andsimilar alkylation reactions of phenols. Examples of suitable catalystsinclude, but are not limited to: boron trifluoride, boron trichoride,and respective complexes with phenol, alcohols, or tetrahydrofuran; zincchloride, aluminum chloride, titanium (III) chloride, titanium (IV)chloride, zirconium (III) chloride, zirconium (IV) chloride, aluminumtrichloride, aluminum phenoxide, reaction product of activated aluminumpowder and CNSL. Boron trifluoride and respective complexes are the mostpreferred among the suitable Lewis acid catalysts because of theirvolatility, which simplify the procedure of catalyst removal from thefinished product. A highly preferred catalyst class is the organicsulfonic acids, due to their moderate strength and activity to promotethe reaction between CNSL-streams and vinyl hydrocarbon monomers. Inaddition, organic sulfonic acids are widely commercially available inhigh purity, they are relatively low cost, and pose less hazardousconditions on handling. More specifically, in respect to themanufacturing processes involving CNSL streams, organic sulfonic acidsoffer the best reaction control, with minimal side reactions, and betterproduct composition uniformity. Examples of suitable organic sulfonicacids are, but not limited to, benzensulfonic acid; ortho-isomer, orpara-isomers of toluenesulfonic acid, or mixture thereof; alpha-isomer,or beta-isomer of naphthalenesulfonic acid, and mixtures thereof;1,5-isomer, or 2,6-isomer of naphthalenedisulfonic acid, and mixturesthereof; nonylphenolsulfonic acid, and mixture of respective isomers;dinonylnaphthylsulfonic acid, and mixture of respective isomers;dodecylbenzenesulfonic acid, methanesulfonic acid;trifluoromethanesulfonic acid, laurylsulfonic acid; phenolsulfonic acidand respective isomers; cresylsulfonic acid, and respective isomers.Preferably, all of the aforementioned sulfonic acids should have about50-100% purity, and more preferably about 95.00-99.99% purity. Thecrystallized hydrate state of all of the aforementioned sulfonic acidsare also suitable catalysts for the manufacture of CNSL-basedhydrocarbon resins.

Solid state or supported acid catalysts are also suitable to promote thereaction between the aforementioned purified and non-purified CNSL andvinyl hydrocarbon monomers. These solid catalysts are insoluble in thereaction media, and generally they are in the form of microbeads, orcoarse particulates, which are designed to have high surface area,improving the conversion rate. The major advantage of these catalystsrelates to the simplification of the process for extraction of the acidcatalyst from the final product by a simple filtration procedure.Conversely, soluble organic catalysts, in general, requireneutralization, and subsequent wash and filtration steps, which canincrease the time and cost of the manufacturing process. These catalystsare very well suited for semi-batch or continuous manufacturingprocesses for the production of CNLS-based hydrocarbon resins. Examplesof suitable solid state or supported acid catalysts include, but are notlimited to, nafion resins, sulfonated poly(styrene-co-divinylbenzene)resins, sulfuric aciddoped silica powder, acid activatedmontmorillonite, activated acid fullers earth, zeolite Y hydrogen form,zeolite ZSM-5 hydrogen form, zeolite beta hydrogen form, Zeolitemordenite hydrogen form, and acid activated bentonite clays.

The type and the amount of catalyst to be used in the manufacturing ofCNSL-based hydrocarbon resins should be carefully selected based on thereactivity of the substrates, and the desired specification of thefinished product. CNSL has the propensity to self-polymerize under theinfluence of strong acid catalysts at high temperatures. Therefore,under these conditions, the resulting CNSL hydrocarbon resin may exhibithigh polymer fraction content as a consequence of these side reactions,which will result in high viscosity of finished products. Very lowlevels of acid catalyst are not satisfactory, because the conversionrate becomes very slow. In addition, the reactivity of the batch can beseriously compromised by the possibility of reaction inhibition(quenching) caused by small unpredictable and unwanted impurities. Forstrong inorganic and Lewis acid catalysts, which exhibit the highercatalytic activity, the optimal catalyst level is about 0.01 to 1.00% ofthe total weight of the reactants, and preferably about 0.05 to 0.2% ofthe total weight. In certain embodiments, the level of strong inorganicacid catalyst or Lewis acid catalyst is about 0.01%, 0.05%, 0.10%,0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90% or 1.00% of thetotal weight of the reactants. Any of these values may be used to definea range for the percentage of the strong inorganic acid catalyst orLewis acid catalyst. For example the percentage of the strong inorganicacid catalyst or Lewis acid catalyst may range from about 0.05% to about0.5%, or from about 0.1% to about 0.5% of the total weight of thereactants. In the case of sulfonic acids, which exhibit moderatecatalytic activity, the optimal catalyst level is about 0.05 to 5.0% ofthe total weight of the reactants, and preferably about 0.3 to 1.0% ofthe total weight.

FIG. 2 illustrates generally the reaction mechanism for one embodimentof the disclosure. As shown in FIG. 2, cardanol may be combined in areactor vessel with a hydrocarbon monomer in the presence ofp-toluenesulfonic acid. The reactor vessel is maintained at atemperature of between 100-120° C. for a period of about 3 hours. Thecardanol and hydrocarbon monomers react to form a CNSL hyrocarbon resin.

Prior to or after the production of CNSL-based hydrocarbon resins,certain additives can be added to attain certain desirable properties,or for better control of the manufacturing process, or to control theintended specifications of the final product.

The molar ratio between the CNSL and the vinyl hydrocarbon resin plays asignificant role on the physico-chemical properties of the resultingresin. More importantly, it can deeply influence the performance of theresin for the intended application. Low [vinyl hydrocarbonmonomer]/[CNSL] molar ratio ranges, such as about 0.8 to 1.8, produceresins with the lowest viscosity, with good compatibility with a varietyof resins and polymer formulations, but reduced color and weatheringstability. Medium [vinyl hydrocarbon monomer]/[CNSL] molar ratio ranges,such as about 1.8 to 3.0, produce resins with intermediate to highviscosity, but they exhibit enhance compatibility, color and weatheringstability. High [vinyl hydrocarbon monomer]/[CNSL] molar ratio ranges,such as above about 3.0, produce resins with high to very highviscosity, and they may exhibit reduced compatibility or phase stabilitywith other resins and polymer formulations, but they have excellentcolor and weathering stability, and enhanced anti-oxidant properties.

In certain embodiments, the molar ratio of the vinyl hydrocarbon monomerto the CNSL in the reaction mixture is about 0.8, 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0 or 10.0. Anyof these values may be used to define a range for the molar ratio of thevinyl hydrocarbon monomer to the CNSL wherein the properties of thedifferent embodiments may have more than one property associated withmore than one molar ratio range. For example, the molar ratio of thevinyl hydrocarbon monomer to the CNSL may range from about 0.8 to 10.0or about 0.8 to 3.0.

The reaction between CNSL and vinyl hydrocarbons is carried out insealed reactors in batch, semi-batch or continuous modes, protected fromexposure to air, and preferably blanketed with an inert or reducingatmosphere. The temperature of reaction is a function of the reactivityof the CNSL, the vinyl hydrocarbon monomer, and the activity of the acidcatalyst. For example, when the vinyl monomer is an aliphatic type and aLewis acid catalyst is used, the temperature range for the process mayrange from about −10° C. to about 90° C., and is preferably betweenabout 40° C. to about 60° C. When the vinyl monomer is an aromatic typeand a Lewis acid catalyst is used, the temperature range for the processmay range from about −10° C. to about 90° C., and is preferably betweenabout 20° C. to about 60° C. When the vinyl monomer is an aromatic typeand an inorganic acid or sulfonic acid catalyst is used, the temperaturerange for the process may range from about 50° C. to about 150° C., andis preferably between about 100° C. to about 120° C.

Even for the combination of substrates with the lowest reactivity, anexothermic reaction is observed at early stages of conversion. As thereactivity of the substrates increase, the temperature of the reactionmust be adjusted to avoid side reactions due to temperature spikes, andthe possibility of runaway reaction at early stages of conversion. TheCNSL streams with relatively higher content of cardol exhibit higherreactivity. The less sterically hindered aromatic vinyl hydrocarbonmonomers are the most reactive ones. Cycloaliphatic and aliphatic vinylhydrocarbon monomers exhibit very low reactivity toward CNSL, and forsuch combination, high catalytic activity is required to achieveadequate conversions. For instance, for the reaction between any aforementioned CNSL streams and styrene or vinyltoluene, the idealtemperature range for high active catalysts, such as borontrifluoride-phenol complex, the ideal reaction temperature is in therange of about −10° to 90° C., and preferably from about 40° to 60° C.For this same combination, but using para-toluenesulfonic acidmonohydrate, the ideal reaction temperature is in the range of about 50°to 150° C., and preferably from about 100° to 120° C.

In certain embodiments the temperature for the reaction between CNSL andvinyl hydrocarbons is about −10° C., 0° C., 10° C., 20° C., 30° C., 40°C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C.,130° C., 140° C., or 150° C. Any of these values may be used to define arange for the temperature for the reaction between CNSL and vinylhydrocarbons. For example, the temperature may range from about −10° C.to about 150° C., about 50° C. to about 150° C., or about 100° C. toabout 150° C.

One embodiment of the process for carrying out the reaction between CNSLand the vinyl hydrocarbon monomer comprises dispersing the catalyst intothe CNSL, followed by slow and controlled addition of the vinyl monomerinto the CNSL/catalyst mixture.

A second embodiment of the process comprises adding at the same time thecatalyst and the vinyl monomer through two different inlet ports (toavoid premature mixing of the catalyst with the vinyl monomer).

A third embodiment comprises dispersing the vinyl monomer into the CNSL,and then slowly adding the catalyst, or a suitable catalyst dispersion,with mixing. In this specific case, at early stages of conversion, thetemperature should be significantly lower than the optimal level toavoid any potential temperature spikes or runaway reaction.

In each of the embodiments described above, the temperature ismaintained in the ranges discussed above depending upon the type ofvinyl monomer and the type of catalyst used.

In another embodiment, CNSL hydrocarbon epoxy resins, specificallyglycidyl ethers of the aforementioned CNSL hydrocarbon resins, can bemade from the reaction between epichlorohydrin and the desired CNSLhydrocarbon resin promoted by strong bases, such as sodium hydroxide orpotassium hydroxide. CNSL hydrocarbon epoxy resins enhances theflexibility, and toughening characteristics of epoxy curingcompositions, such as protective coatings, adhesives, and composites,without compromising the mechanical properties, compatibility, weatherand chemical resistance. This feature makes them very advantageous overthe traditional long aliphatic glycidyl ethers, which also promotes goodflexibility, and toughening characteristics but at expense of reducedoverall performance.

As noted in previous inventions [Process for manufacture of glycidylethers of polyhydric phenols, U.S. Pat. No. 2,801,227 A; and Preparationof liquid epoxy resins from bisphenols, U.S. Pat. No. 4,132,718 A], theuse of a large stoichiometric excess of epichlorohydrin, and controllingthe amount of water and the pH in the reaction medium also play acrucial role in minimizing side reactions that lead to significantamounts of undesirable inactive side products, high viscosity, low epoxyequivalent weight values, and high concentration of compounds withhydrolysable chlorine fragments.

Alternatively, CNSL hydrocarbon epoxy resins can be made from theepoxidation reaction of the allyl ethers of the desired CNSL hydrocarbonresin with inorganic or organic peroxides, or mixtures of hydrogenperoxide and carboxylic acids, such as acetic or formic acids. In turn,the referred allyl ethers of CNSL hydrocarbon resins can be made by thereaction between any aforementioned CNSL hydrocarbon resin and allylchloride promoted by inorganic bases, such as sodium hydroxide orpotassium hydroxide. Allyl bromide and allyl iodide are also suitableand more reactive alternatives to allyl chloride. The epoxidation ofCNSL hydrocarbon resin allyl ethers may occur not only on the intendedallyl group, but the unsaturations of the side chain can also beepoxidized all together. The allyl ether groups are more reactive, andhence more prone to epoxidation by organic and inorganic peroxides thanthe side chain double bonds of the CNSL building blocks. Therefore thedegree of epoxidation can be controlled by the reaction conditions andthe stoichiometric ratio of the reactants.

In another embodiment, alkoxylated CNSL hydrocarbon epoxy resins can bemade from the reaction between any aforementioned CNSL hydrocarbon resinand an alkelene or cycloalkelene oxide promoted by acid or basecatalysts under high temperature and pressure. The resulting alcohol orpolyol are suitable for the 1-part or 2-part polyurethane systems usedin semi-flexible and rigid foams, building materials, and adhesives.These polyurethane-polyols systems are very hydrophobic, and exhibitgood mechanical behavior that is comparable to a great number ofconventional aromatic polyether polyesters, in addition to improvedimpact resistance and flexibility. Examples of alkelene oxide include,but not limited to, ethylene oxide, propylene oxide, cyclohehane oxide,dicyclopentadiene diepoxide, and styrene oxide. The process foralkoxylation of CNSL hydrocarbon epoxy resins involves slow addition ofalkelenes oxides to a mixture of CNSL hydrocarbon resin and catalyst attemperature in between 80 and 220° C., more preferably between 150 and180° C., and under pressure of 10-150 psi, more preferably between 30-75psi, and catalyzed by inorganic base, such as sodium hydroxide, orpotassium hydroxide. The stoichiometric ratio between CNSL hydrocarbonresin and the alkelene oxide is judiciously chosen based on thedesirable amount of alkelene oxide monomeric units appended to thehydroxyl groups of CNSL hydrocarbon resin. Large alkelene oxide to CNSLhydrocarbon resin equivalent ratios produce resins with long chains ofpolyalkene oxide appended to the CNSL hydrocarbon resins, which mayrender surfactant properties to the final product. Hence, surfactant issuitable for pigment dispersion aid, and rheology modifier in paintformulations.

Alternatively, ethoxylated or propoxylated CNSL hydrocarbon polyolresins can be made by reacting any aforementioned CNSL hydrocarbon resinwith ethylene carbonate or propylene carbonate respectively, using thesimilar established manufacturing procedure for ethoxylated of plaincardanol [Cardanol derivative and method of making the cardanolderivative EP 1137620 A1]. This reaction is catalyzed by an organic orinorganic base. This procedure offers an advantage over traditionalalkoxylation with organic oxides because it can be run at normalpressure, which simplifies the basic manufacturing equipmentrequirements. The most commonly catalysts employed for this specificmechanism of alkoxylation reactions are volatile organic amines, becausethey are very effective, and they can be easily removed from thereaction product by simple vacuum distillation. The reaction betweenCNSL hydrocarbon resin and ethylene or propylene carbonate is conductedat 100-220° C., more preferably between 150-180° C., and the amount ofcatalyst is generally between 0.1 to 10% of the total charge ofreactants, but more preferably between 1-3%.

The following examples provide exemplary embodiments of the presentinvention, and the examples are not intended to limit the scope of theinvention in any way.

EXAMPLES Example 1 Pure CNSL—Alphamethylstyrene Resin

A 1 L round bottom multi-neck glass flask, equipped with a thermometer,a condenser, a mechanical stirrer, and an inlet port controlled by aperistaltic pump, was charged with 300 g or 1.0 mol of distilled CNSL(NX-4708M, Cardolite Co.). The whole set up was continually purged witha gentle flow of pure dry nitrogen. The temperature of the flaskcontents was raised to 80° C., and then 3.0 g of purepara-toluenesulfonic acid were added to the flask. Upon dispersion ofthe acid catalyst, 300 g or 2.54 mol of alpha-methylstyrene (AcrosChemicals Co, 98% pure) were added to the reaction mixture via theperistaltic pump, while the content of the flask was vigorously stirred.As soon as the addition started, the temperature was allowed to slowlyrise up to 120° C. The addition rate of the styrene was adjusted to takeabout 15 minutes to completion. Then, the reaction mixture was allowedto react for an additional 120 minutes. The non-reactedalpha-methylstyrene was vacuum distilled using an oil pump, at 0.05mmHg. The resin was dispensed as is without any further purificationstep.

The yield was 552 g of resin having the following properties: BrookfieldViscosity (300 rpm, 25° C., spindle #3)=358 cPs; Gardner color=10; freealpha-methylstyrene (by GC)=0.04%; free cardanol (by HPLC)=4.7%

Example 2 Hydrogenated CNSL—Vinyltoluene Resin

A 1 L round bottom multi-neck glass flask, equipped with a thermometer,a condenser, a mechanical stirrer, and an inlet port controlled by aperistaltic pump, was charged with 304 g or 1.0 mol of hydrogenated anddistilled CNSL (NC-510, Cardolite Co.). The whole set up was continuallypurged with a gentle flow of pure dry nitrogen. The temperature of theflask contents was raised to 80° C., and then 3.0 g of purepara-toluenesulfonic acid were added to the flask. Upon dispersion ofthe acid catalyst, 312 g or 3.0 mol of vinyltoluene (Acros Chemicals Co,98%, mixture of isomers) were added to the reaction mixture via theperistaltic pump, while the content of the flask was vigorously stirred.As soon as the addition started, the temperature was allowed to rise upto 120° C. The addition rate of the vinyltoluene was adjusted to takeabout 15 minutes to completion. Then, the reaction mixture was allowedto react for an additional 60 minutes. The non-reacted vinyltoluene wasvacuum distilled using an oil pump, at 0.05 mmHg. The resin wasdispensed as is without any further purification step.

The yield was 605 g of resin having the following characteristics:Brookfield Viscosity (300 rpm, 25° C., spindle #3)=2640 cPs; Gardnercolor=<1; free styrene (by GC)=0.04%; free hydrogenated cardanol (byHPLC)=0.25%

Example 3 Ultra-High Pure CNSL—Styrene Resin

A 500 mL round bottom multi-neck glass flask, equipped with athermometer, a condenser, a mechanical stirrer, and an inlet portcontrolled by a peristaltic pump, was charged with 150 g or 0.5 mol ofhighly purified CNSL with cardol content lower than 0.1% (GX-2512,Cardolite Co.). The whole set up was continually purged with a gentleflow of pure dry nitrogen. The temperature of the flask contents wasraised to 80° C., and then 1.5 g of pure para-toluenesulfonic acid wereadded to the flask. Upon dispersion of the acid catalyst, 104 g or 1.0mol of Styrene (Acros Chemicals Co, 99.9% pure, stabilized with 0.1%TBC) were added to the reaction mixture via the peristaltic pump, whilethe content of the flask was vigorously stirred. As soon as the additionstarted, the temperature was allowed to rise up to 100° C. The additionrate of the styrene was adjusted to take about 45 minutes to completion.Then, the reaction mixture was allowed to react for an additional 90minutes. The non-reacted styrene was vacuum distilled using an oil pump,at 0.05 mmHg. Then, a solution of 2.0 g of sodium bicarbonate (AcrosChemicals Co) in 50 mL of distilled water were added to neutralize thecatalyst. The waste was vacuum distilled, and the resulting hazy oil wastreated with filtration aid ceramic and filtered through a frittedfunnel under vacuum.

The yield was 232 g of resin having the following properties: BrookfieldViscosity (300 rpm, 25° C., spindle #3)=455 cPs; Gardner color=3; freestyrene (by GC)=0.07%; free cardanol (by HPLC)=1.9%

Example 4 Pure CNSL—Divinylbenzene Resin

A 1 L round bottom multi-neck glass flask, equipped with thermometer, acondenser, a mechanical stirrer, and an inlet port controlled by aperistaltic pump, was charged with 300 g or 1.0 mol of distilled CNSL(NX-4708, Cardolite Co.). The whole set up was continually purged with agentle flow of pure dry nitrogen. The temperature of the flask contentswas raised to 100° C., and then 2.5 g of pure para-toluenesulfonic acidwere added to the flask. Upon dispersion of the acid catalyst, 195 g or1.5 mol of Divinylbenzene (TCI America Co, mixture of meta-, andpara-isomers, also containing 40% ethylvinylbenzene) were added to thereaction mixture via the peristaltic pump, while the content of theflask was vigorously stirred. As soon as the addition started, thetemperature was allowed to rise up to 140° C. The addition rate of thedivinylbenzene was adjusted to take about 30 minutes to completion.Then, the reaction mixture was allowed to react for an additional 30minutes. The non-reacted vinyl monomers were vacuum distilled using anoil pump, at 0.05 mmHg. The resin was dispensed as is without anyfurther purification step.

The yield was 485 g having the following characteristics: BrookfieldViscosity (100 rpm, 25° C., spindle #3)=6035 cPs; HPLC/GPC results:Mn=1,384 g/mol, Mw=2,241 g/mol, polymer dispersity=1.62; freecardanol=0.8%.

Example 5 Glycidyl Ethers of CNSL Hydrocarbon Resin

A 1000 mL round bottom multi-neck glass flask, equipped with athermometer, a condenser, a mechanical stirrer, and an inlet port with aaddition funnel with pressure equalizer feature, was charged with 336 g(1 equivalent-weight. based on hydroxyl group content) of styrenatedultra-high pure CNSL resin described in example 3, and 222 g (4equivalent-weight) of epichlorohydrin, and the resulting mixture wasstirred for stirred and warmed up to 65° C. in 30 minutes. Then, 52.8 g(1 equivalent weight) of a 50% by weight solution of sodium hydroxide inwater were added via the addition funnel over 3 hours period. Meanwhilethe water-epichlorohydrin azeotrope from the reaction mixture wasdistilled under vacuum at 150-170 mmHg out to a Dean-Stark trap, inwhich the condensed epichlorohydrin-water heterogenous mixture wasdecanted, and the epichlorohydrin layer was allowed to return to thereaction flask. Upon completion the addition of epichlorohydrin, thereaction mixture was stirred at 68-72 hours for one additional hour.Then, the excess of epichlorohydrin was removed from the reactionmixture by vacuum distillation at 70-90° C. and 100 mmHg. The resultingthick slurry was then extracted with a mixture of 100 g of xylenes and100 g of water. The aqueous phase was decanted out, and the organicphase was filtered and evaporated under vacuum to remove xylenes. Theresulting light color oil was then filtered through a short plug ofCelite filtration aid.

The yield was 365 g having the following characteristics: BrookfieldViscosity (100 rpm, 25° C., spindle #3)=609 cPs; Gardner color=6; Epoxyequivalent weight=618, hydrolizable chlorine content=0.18%.

Example 6 Ethoxylated CNSL Hydrocarbon Resin

A 1000 mL round bottom multi-neck glass flask, equipped with athermometer, a condenser, and a mechanical stirrer, was charged with 336g (1 equivalent-weight. based on hydroxyl group content) of styrenatedultra-high pure CNSL resin described in example 3, and 4.9 g (0.08equivalent-weight) of triethylamine as a catalyst, and the resultingmixture was stirred under nitrogen and heated up to 155° C. Then, 58.1 g(1.1 equivalent weight) of molten ethylene carbonate were added to theflask over 3 hours period. Once completed the addition, the batch wasstirred for another hour at 155° C., followed by vacuum distillation at80-85° C. and 100 mmHg to remove any unreacted ethylene carbonate andtriethylamine.

The yield was 362 g having the following characteristics: BrookfieldViscosity (100 rpm, 25° C., spindle #3)=655 cPs; Gardner color=7;Hydroxyl value=109 mgKOH/g.

Example 7 Application

The ability of CNSL hydrocarbon resin (from Example 3) to reduce theviscosity of liquid epoxy at different concentrations was investigated(e.g., viscosity reduction property). Six systems were tested in whichthe percentage of CNSL hydrocarbon resin in Epon 828 was 5%, 10%, 15%,20%, 25% or 30%. The viscosities of the six systems were measured byusing a CAP 2000+VISCOMETER (BYK). Similar systems using a commercialphenol-hydrocarbon resin were tested for comparison.

As shown in Table 1 below and FIG. 3, use of CNSL hydrocarbon resin as adiluent resulted in a greater reduction in viscosity of the liquid epoxyin comparison to the commercial phenol-hydrocarbon resin.

TABLE 1 Viscosities of Liquid Epoxy and Hydrocarbon Resin BlendsViscosities of liquid epoxy and hydrocarbon Percentage of resin blends@25° C./cps hydrocarbon With commercial With CNSL resin in liquidphenol-modified hydrocarbon resin epoxy hydrocarbon resin (from Example3)  0% 14280 14280  5% 10650 9165 10% 10031 7512 15% 9638 6313 20% 91505575 25% 8588 4853 30% 8156 4313

Investigation of Persoz hardness development was performed on a clearcoating system (no pigment, additive and solvent added). A liquid epoxyEpon 828 and curing agent Versamid 115×70 system was used atstoichiometric ratio. 30% CNSL hydrocarbon resin or phenol-hydrocarbonresin (based on the weight of liquid epoxy) was evaluated.

For the Persoz hardness measurement, the testing panels were prepared bya BYK 15 Mirs wet application bar over QD-36 cold rolled steel panels(Q-panel, 3″×6″×0.020″). Persoz hardness numbers were obtained by usinga Pendulum hardness tester (BYK Gardner) based on ASTM D 4366.

As shown in Table 2 below, the Persoz hardness results indicated thatthe system with 30% CNSL hydrocarbon resin gave faster cure property incomparison to the one with commercial hydrocarbon resin.

TABLE 2 Persoz hardness development of different systems at 25° C. curecondition Persoz hardness/sec. With commercial With CNSL Cure time @phenol-modified hydrocarbon resin 25° C./day hydrocarbon resin (fromExample 3) 2 30 40 5 125 149 9 168 187

The adhesion tape test (ASTM D 3359-97) was performed on rusted S-36panels (Q-panel, 3″×6″0.020″) (adhesion over rust metal substrate). Toobtain a uniform rusted surface, the clean S-36 panels were immersed ina 60° C. water bath (Precision circulating water bath, Model 260) for 24hours followed by a warm tap water rinsing to remove the loosened rust.The panels were roughly dried with a paper towel and stored at roomtemperature for seven days before use.

TABLE 3 Pigmented white epoxy base formulation Composition Gray epoxybase (grams) Liquid epoxy 30 CNSL hydrocarbon resin 6 (from Example 3)Dispersant 3 Extender 65 pigment 13 Solvent 7.5 Flow control 0.6 Totalof white epoxy base 125.1 Curing agent 44.7

Pigmented systems were applied over the rusted panels via a 10 Mirs wetapplication bar. After a seven-day room temperature cure, the crosshatch adhesion test was performed. As shown in FIG. 4, there was 100%adhesion with no failure. The addition of CNSL hydrocarbon resin tocoating system gave good adhesion property to rust metal substrate.

Salt spray exposure (ASTM B117) was evaluated based on the sameformulation shown in Table 3 (anti-corrosion property). As shown if FIG.5, after 668 hours salt spray exposure, the test panel with 20% CNSLhydrocarbon resin exhibited no rust underneath the coating film exceptfor a few small blisters near the scribed lines.

The invention claimed is:
 1. A resin comprising: a) about 20% to about95% by weight of vinylated cardanols and vinylated cardols; and b) about1% to about 40% by weight of hydrocarbon cyclic dimers.
 2. The resin ofclaim 1, further comprising about 1% to about 50% by weight of one ormore additional polymers.
 3. The resin of claim 2, wherein the one ormore additional polymers are linear chains composed of vinyl hydrocarbonmonomers or cardanol polymers.
 4. The resin of claim 3, wherein thelinear oligomers have a degree of polymerization of no less than 2 andno more than 10 repeating monomer units.
 5. A reaction mixturecomprising: a) Cashew Nut Shell Liquid (CNSL); and b) a vinylhydrocarbon.
 6. The reaction mixture of claim 5, further comprising anacid catalyst.
 7. The reaction mixture of claim 6, wherein the acidcatalyst is a Lewis acid.
 8. The reaction mixture of claim 5, whereinthe vinyl hydrocarbon is an aliphatic vinyl monomer or an aromatic vinylmonomer.
 9. The reaction mixture of claim 6, wherein the vinylhydrocarbon is an aromatic vinyl monomer and the acid catalyst is aninorganic acid or a sulfonic acid.
 10. The reaction mixture of claim 6,wherein the vinyl hydrocarbon is alpha-methylstyrene acid and thecatalyst is para-toluenesulfonic acid.
 11. A process for manufacturing aCashew Nut Shell Liquid (CNSL) hydrocarbon resin comprising the stepsof: (a) adding to a reactor vessel a quantity of CNSL; (b) adding anacid catalyst to the CNSL; (c) adding a vinyl hydrocarbon monomer to theacid catalyst and CNSL; and (d) maintaining the reactor vessel at apredetermined temperature for a predetermined period of time, therebyproducing the CNSL hydrocarbon resin.
 12. The process of claim 11,wherein the acid catalyst is a Lewis acid.
 13. The process of claim 11,wherein the vinyl hydrocarbon monomer is an aliphatic vinyl monomer oran aromatic vinyl monomer.
 14. The process of claim 12, wherein thevinyl hydrocarbon monomer is an aromatic vinyl monomer and the catalystis an inorganic acid or a sulfonic acid.
 15. The process of claim 12,wherein the vinyl hydrocarbon monomer is alpha-methylstyrene and thecatalyst is para-toluenesulfonic acid.
 16. The process of claim 11,further comprising catalytically reducing the CNSL with hydrogen underpressure and in the presence of an active metal catalyst prior to addingthe CNSL to the reactor vessel.
 17. The process of claim 11, furthercomprising reacting the CNSL hydrocarbon resin with an aldehyde orketone to form a CNSL-novolac resin.
 18. The process of claim 11,further comprising reacting the CNSL hydrocarbon resin withepichlorohydrin in the presence of a base to produce a glycidyl ether ofthe CNSL hydrocarbon resin.
 19. The process of claim 11, furthercomprising reacting the CNSL hydrocarbon resin with an alkelene orcycloalkelene oxide in the presence of an acid or base catalyst underhigh temperature and pressure to produce an alkoxylated CNSL hydrocarbonepoxy resin.
 20. The process of claim 11, further comprising reactingthe CNSL hydrocarbon resin with ethylene carbonate or propylenecarbonate in the presence of an organic or inorganic base.
 21. Theprocess of claim 11, further comprising reducing the CNSL hydrocarbonresin with pressurized hydrogen in the presence of a catalyst.
 22. Theprocess of claim 11, wherein the molar ratio of the vinyl hydrocarbonmonomer and the CNSL is from about 0.8 to about 5.0.
 23. The process ofclaim 11, wherein the temperature is from about −10° C. to about 150° C.